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WO2008128826A1 - Particules contenant un matériau photocatalytique - Google Patents

Particules contenant un matériau photocatalytique Download PDF

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Publication number
WO2008128826A1
WO2008128826A1 PCT/EP2008/052996 EP2008052996W WO2008128826A1 WO 2008128826 A1 WO2008128826 A1 WO 2008128826A1 EP 2008052996 W EP2008052996 W EP 2008052996W WO 2008128826 A1 WO2008128826 A1 WO 2008128826A1
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WO
WIPO (PCT)
Prior art keywords
acid
weight
textiles
preferred
oil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2008/052996
Other languages
German (de)
English (en)
Inventor
Matthias Sunder
Georg Meine
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of WO2008128826A1 publication Critical patent/WO2008128826A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0063—Photo- activating compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
    • D06M10/06—Inorganic compounds or elements
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form

Definitions

  • the present invention relates to particles and granules which contain a) photocatalytic material, b) support material and c) organic solvent. Furthermore, it relates to detergents or cleaners which contain such particles and / or granules. Furthermore, it relates to a process for the preparation of these particles and granules. It further relates to a method of applying fine particulate photocatalytic material to textiles and hard surfaces. It further relates to various processes for the cleaning, care, finishing, softening and / or conditioning of textiles by treating these articles in a treatment bath using the particles, granules or detergents according to the invention, at and / or followed by exposure of the article Light in the wavelength range of 10-1200 nm.
  • photocatalytic materials to control soil and / or unwanted microorganisms is desirable because the photocatalytic material may utilize electromagnetic radiation of a suitable wavelength range to degrade or deactivate debris and / or unwanted microorganisms by photocatalytic or photochemical reaction.
  • suitable photocatalytic material is very finely divided substances, for example in the size range of at least ⁇ 500 nm.
  • the object of the present invention was therefore to enable the homogeneous incorporation of finely divided photocatalytic material into solid detergent matrices.
  • a particle comprising a) photocatalytic material, b) carrier material and c) organic solvent.
  • the particles according to the invention are suitable for being part of a washing or cleaning agent.
  • the particles according to the invention can also be independent washing or cleaning agents.
  • This item offers two immediate benefits. First, it allows for improved handling and metering of the photocatalytic material as it is now in a "dilute" form.
  • the photocatalytic material used retains its activity because it no longer causes unwanted self-agglomeration phenomena of the photocatalytic material, e.g. due to storage and segregation, which would mean a loss of photocatalytic activity.
  • the incorporation of the finely divided photocatalytic material into the solid support is accompanied by a very good storage stability, which also relates to the entire detergent into which the particles according to the invention can be incorporated.
  • This is an advantage in terms of possible decomposition processes that could otherwise result from the activity of the photocatalytic material in the detergent matrix.
  • the use of the particles according to the invention in the textile treatment also enables a uniform mounting of the photocatalytic material on the textiles to be treated.
  • the dust load during detergent production can be reduced.
  • the particles according to the invention also enable a textile-sparing textile treatment, for example stain treatment.
  • the contained photocatalytic material uses electromagnetic radiation of a suitable wavelength range, by virtue of which e.g. Soils or microbes by photocatalytic or photochemical reaction, e.g. by oxidation or reduction, degradable, deactivatable or reducible.
  • the photocatalytic material is in particular a daylight-active material, in particular a daylight-active bleach, thus uses the electromagnetic radiation of daylight.
  • the presence of preferably oxygen and / or water is required.
  • the photocatalytic activity of the photocatalytic material advantageously relates to natural or artificial light in the wavelength range of 10-1200 nm, preferably 300-1200 nm, in particular between 380 and 800 nm. If the photocatalytic material in particular visible to the human eye radiation of the visible region of the Spectrum with wavelengths between 380 and 800 nm for the above-mentioned Exploits the purpose of degradation, deactivation or reduction of impurities, then there is a preferred embodiment of the invention. Also UV light (10-380 nm) is very beneficial.
  • the photocatalytic material can be effective in several ways during and after the textile treatment.
  • the textiles to be treated are placed in a tub containing a wash liquor into which particles of the present invention have been added, and then exposed to light, for example, sun exposure, then the photocatalytic material in the fabric treatment bath exhibits a general cleaning performance .
  • the photocatalytic material which is applied to the textiles to be dried in the course of the textile treatment, is capable of interacting with a light irradiation, eg. by sunlight when drying on a leash outdoors, to develop a general cleaning performance. Such is also possible in the textile drying in an automatic clothes dryer with internal light source.
  • the dried textiles are not really dry in the true sense, but contain a residual moisture, which is in balance with the ambient humidity (room humidity, body moisture). These conditions are sufficient to develop a general cleaning performance, caused by the deposited on the textiles photocatalytic material under light irradiation, for example by sunlight.
  • This latter effect is particularly advantageous because the treated garments are provided with a long-term protection, so that the clothing is equipped with a self-cleaning ability.
  • This self-cleaning power is advantageous, for example, to counteract the development of fetid odors, which quickly form on clothing, for example after sweat-inducing activities (eg sports activities).
  • This self-cleaning capability is advantageous, for example, to prevent or at least complicate the colonization of microbes on textiles.
  • This self-cleaning capability is advantageous, for example, to prevent or aggravate the build-up and sticking of, in particular, colored stains on fibers.
  • the photocatalytically active material is advantageous in order to improve the Wiederschwasberry of colored stains.
  • the photocatalytically active material is capable of destroying the structure of, in particular, colored stains (dyes), for example by oxidation, under the action of light.
  • the conjugated double bonds, which are responsible for the absorption of visible light in the dyes and thus for the coloring, are cleaved or hydroxylated.
  • the dye loses its coloring properties and also its strong fiber adhesion.
  • Noxa is understood to mean factors that can damage the human organism, or at least impair people's well-being. These are in particular the just mentioned factors, especially microbiological factors such as viruses, bacteria, fungi, etc.
  • the development of the overall cleaning effect which can be observed in the use of the particles of the present invention is particularly effective with respect to colored impurities, in particular due to red to blue anthocyanin dyes, e.g. Cyanidin, e.g. from cherries or blueberries, red betanidine from beetroot, orange-red carotenoids, e.g. Lycopene, beta-carotene, e.g. from tomatoes or carrots, yellow curcuma dyes, e.g. Curcumin, e.g. curry and mustard, brown tannins, e.g. from tea, fruit, red wine, deep brown humic acid, e.g.
  • red to blue anthocyanin dyes e.g. Cyanidin, e.g. from cherries or blueberries, red betanidine from beetroot, orange-red carotenoids, e.g. Lycopene, beta-carotene, e.g. from tomatoes or carrots, yellow curcuma dyes, e
  • quick action is the top priority, because the fresher a stain, the easier it is to remove.
  • a drying of stains or other contaminants, such as blood, coffee, tea, pen, fruit, red wine or tar stains, especially over several days should usually be avoided so that it does not come to a possibly irreversible fiber adhesion.
  • the present invention provides relief because fabrics treated with detergents containing the particles of the present invention have demonstrated that the fiber adhesion of stains or other contaminants has been so attenuated that they have been more easily washed out.
  • the described advantages also extend to the cleaning of hard surfaces.
  • the particles according to the invention contain an organic solvent.
  • the organic solvent comprises at least one nonionic surfactant, preferably from the group consisting of the alkoxylated fatty alcohols, the alkylphenol polyglycol ethers, the alkoxylated fatty acid alkyl esters, the polyhydroxy fatty acid amides, the alkyl glycosides, the alkyl polyglucosides, the amine oxides of the fatty acid glucamides and / or the long-chain alkyl sulfoxides, a preferred embodiment of the present invention Invention.
  • a predominant part of the organic solvent consists of nonionic surfactant (s), preferably the organic solvent contains> 50% by weight, advantageously> 60% by weight, more preferably> 70 Wt .-% and in particular> 80 wt .-% of nonionic surfactant, wherein the statement wt .-% based on the total amount of the organic solvent. It is even possible that> 90% or even 100% of the total organic solvent is nonionic surfactant (s).
  • organic solvents include alkoxylated fatty alcohol.
  • the organic solvent contains alkoxylated fatty alcohol, preferably in amounts of at least 40 wt .-%, advantageously of at least 50 wt .-%, more preferably of at least 60 wt .-%, most advantageously of at least 70 wt.
  • the organic solvent which are advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18, in particular 12 to 18 carbon atoms and preferably on average 1 to 12 moles of alkylene oxide, preferably ethylene oxide, per mole of alcohol, in particular 7 moles of ethylene oxide per mole of alcohol a preferred embodiment of the invention.
  • the organic solvent comprises at least one alkoxylated fatty alcohol
  • a particularly good storage stability of the particles according to the invention results. This also applies to detergent matrices into which the particles can be incorporated.
  • a particularly good, uniform Aufzieh the photocatalytic material was observed in the washing application.
  • the organic solvent comprises at least one humectant, preferably glycerol, dimers and trimers of glycerol, ethylene glycol, propylene glycol, sugar alcohols such as preferably glucitol, xylitol, mannitol, alkylpolyglucosides, fatty acid glucamides, sucrose esters, sorbitans, polysorbates, polydextrose, polyethylene glycol, preferably with middle ones Molecular weights of 200 to 8000, propanediols, butanediols, triethylene glycol, hydrogenated glucose syrup and / or mixtures of the above, preferably in amounts of 0.01 to 50 wt .-%, advantageously 0.1 to 40 wt .-%, in a further advantageous manner 1-30 wt .-%, more preferably 2-20 wt .-%, in particular 5 to 15 wt .-%, based on the total amount of the organic solvent, so there is also a preferred embodiment
  • organic solvents containing 85-95% by weight of nonionic surfactant, preferably alkoxylated fatty alcohol, and 5-15% by weight of humectant, preferably glycerol, may be preferred.
  • organic solvents are preferred which consist only of nonionic surfactant and humectant.
  • the organic solvent comprises at least one organic humectant
  • a particularly suitable humectant is glycerin as well as its dimers and trimers and / or mixtures thereof.
  • the support material according to the invention preferably comprises inorganic material, in particular zeolite, sulfate, carbonate, silicate, clay, silicic acid and / or mixtures thereof. This corresponds to a preferred embodiment of the invention.
  • the particles according to the invention contain alkyl polyglucoside in an amount of 0.1-40% by weight, based on the total organic solvent.
  • inorganic material advantageously zeolite, in particular zeolite X, Y, A, P, MAP and / or mixtures thereof, wt .-% based on the total support material, so again is a preferred embodiment of the invention.
  • Spray drying is a long-established process that is also used in the production of powdered detergents.
  • the first step of the process is the preparation of an aqueous slurry of thermally stable (detergent) ingredients which preferably do not volatilize or decompose under spray drying conditions (eg, surfactants, builders, sizing agents).
  • the slurry is then pumped into a spray tower and sprayed through nozzles located in the top of the tower.
  • the sprayed slurry is then dried by rising air at a temperature of preferably 200 to 35O 0 C and the adhering water is thereby evaporated so that the ingredients used are obtained at the outlet of the tower as fine powders.
  • the particles according to the invention as support material thus comprise a spray-dried powder, preferably containing
  • (A) inorganic support material preferably comprising zeolite, sulfate, carbonate, silicate, clay, silica and / or mixtures thereof, preferably in amounts of> 30 wt .-%, advantageously> 40 wt .-%, more preferably> 50 wt .-%, more preferably> 60 wt .-%, in particular 70-90 wt .-%,
  • nonionic surfactant in particular ethoxylated fatty alcohol, advantageously in amounts of 0.1-40 wt .-%. In particular 0.5-5% by weight
  • graying inhibitor preferably carboxymethylcellulose sodium salt, preferably in amounts of 0-10% by weight, in particular 1-5% by weight,
  • (E) optionally alkalis, preferably the hydroxides of the alkali metals, in particular sodium hydroxide and / or potassium hydroxide, wt .-% in each case based on the carrier material, so is a further preferred embodiment of the invention.
  • the photocatalytic material comprises titanium dioxide, in particular a modified titanium dioxide, preferably a carbon-modified titanium dioxide.
  • the photocatalytic material in particular the (preferably modified) titanium dioxide, according to a preferred embodiment of the invention in the particles according to the invention in amounts of advantageously 0.0001 to 30 wt .-%, preferably 0.001 to 20 wt .-%, advantageously 0.01 to 15 wt .-%, in a further advantageous manner 0.1 to 10 wt .-%, more preferably 1 to 5 wt .-%, wt .-% based on the total particles.
  • the (preferably modified) titanium dioxide is a carbon-modified titanium dioxide.
  • it can be different too modified titanium dioxides are used, for example, with nitrogen-modified titanium dioxide or, for example, doped with rhodium and / or platinum ions titanium dioxide.
  • the carbon content of the advantageously carbon-modified titanium dioxide may in a preferred embodiment in the range of 0.01 to 10 wt .-%, preferably from 0.05 to 5.0 wt .-%, advantageously from 0.3 to 1, 5 wt. %, in particular from 0.4 to 0.8% by weight.
  • the TiO 2 content of the carbon-modified titanium dioxide is, for example, more than 95% by weight, 96% by weight, 97% by weight, 98% by weight or 99% by weight, based on the total with carbon modified titanium dioxide.
  • the modified titanium dioxide may advantageously additionally contain nitrogen.
  • the specific surface of the titanium dioxide preferably of the modified titanium dioxide, according to BET (BET advantageously determined according to DIN ISO 9277: 2003-05, preferably also simplified according to DIN 66132: 1975-07) preferably 50 to 500 m 2 / g, advantageously 100 to 400 m 2 / g, in a further advantageous manner 200 to 350 m 2 / g, in particular 250 to 300 m 2 / g, so is also a preferred embodiment.
  • the carbon-modified titanium dioxide can be obtained according to a preferred embodiment, for example, by intimately mixing a titanium compound having a specific surface area of preferably at least 50 m 2 / g according to BET, with an organic carbon compound and the mixture at a temperature of up to is thermally treated to 35O 0 C.
  • the carbonaceous substance which can be used in this case can, according to a preferred embodiment, be a carbon compound which contains at least one functional group, preferably selected from OH, CHO, COOH, NHx, SHx.
  • the carbon compound may be a compound selected from ethylene glycol, glycerol, succinic acid, pentaerythritol, carbohydrates, sugars, starch, alkyl polyglucosides, organoammonium hydroxides or mixtures thereof. It is also possible for carbon black or activated carbon to be used as the carbonaceous substance.
  • the carbonaceous substance which is advantageously mixed with the titanium compound, after the thermal treatment to the modified titanium dioxide, a decomposition temperature of at most 400 0 C preferably ⁇ 35O 0 C and particularly preferably ⁇ 300 0 C has.
  • the titanium compound which is preferably used for producing the modified titanium dioxide and intimately mixed with an organic carbon compound according to the aforementioned preferred embodiment may be an amorphous, partially crystalline or crystalline titanium oxide or hydrous titanium oxide or a titanium hydrate or a titanium oxyhydrate, which in turn corresponds to a preferred embodiment ,
  • the thermal treatment of the mixture of the titanium compound and the carbon compound can, according to a preferred embodiment, advantageously be carried out in a continuously operated calcining unit, preferably a rotary kiln.
  • the modified titanium dioxide is preferably derivable e.g. obtained by reacting a titanium dioxide (eg having a particle size in the range from 2 to 600 nm or eg 3 to 150 nm or eg 4 to 100 nm or eg 5 to 75 nm or eg 10 to 30 nm or eg 200 to 400 nm) , such as commercially available in powder or slurry form, and from which produces a suspension in a liquid, such as preferably water.
  • a titanium dioxide eg having a particle size in the range from 2 to 600 nm or eg 3 to 150 nm or eg 4 to 100 nm or eg 5 to 75 nm or eg 10 to 30 nm or eg 200 to 400 nm
  • a carbonaceous substance is then advantageously added to the suspension.
  • Mixing can be assisted by the use of ultrasound.
  • the mixing process e.g., stirring
  • the mixing process may preferably last several hours, preferably 2, 4, 6, 8, 10 or 12 hours or even longer.
  • the amount of the carbon compound is advantageously 1-40% by weight, accordingly, the amount of the titanium compound is preferably 60-99% by weight.
  • the liquid is removed, for example by filtration, evaporation in vacuo or decantation, and the residue is preferably dried (eg, preferably at temperatures of 70-200 0 C, advantageously over several hours, for example at least 12 hours) and then calcined, for example a temperature of at least 26O 0 C, preferably for example at 300 0 C, preferably over a period of several hours, preferably 1-4 hours, in particular 3 hours.
  • the calcination may advantageously take place in a closed vessel.
  • the calcination temperature for example 300 0 C, is reached within one hour (slow heating to 300 0 C).
  • a color change of the powder from white to dark brown to beige or slightly yellowish-brownish is preferably observed. Too long a heating leads to inactive, colorless powders. The expert can estimate this with a few routine experiments.
  • the calcination can eg advantageously take place until after a color change of the powder from white to dark brown another color change takes place on beige or slightly yellowish-brownish.
  • a maximum temperature of 35O 0 C should preferably not be exceeded.
  • decomposition of the organic carbon compound occurs on the surface of the titanium compound, so that it is preferable to form a modified titanium dioxide containing preferably 0.005-4% by weight of carbon.
  • the product is advantageously deagglomerated by known methods, for example in a pin mill, jet mill or counter-jet mill.
  • the grain fineness to be achieved depends on the grain size of the starting titanium compound.
  • the particle size or specific surface area of the product is only slightly lower, but of the same order of magnitude as that of the educt.
  • the desired grain fineness of the photocatalyst depends on the field of application of the photocatalyst. It is usually in the range as with TiO 2 pigments, but may also be below or above.
  • the photocatalytic material, preferably modified titanium dioxide, contained in the particle according to the invention may advantageously have a particle size in the range between 2 and 600 nm, ie e.g. 3 to 150 nm or e.g. 4 to 100 nm or e.g. 5 to 75 nm or e.g. 10 to 30 nm or e.g. 200 to 400 nm.
  • the particle size of the photocatalytic material, preferably modified titanium dioxide may preferably be in the range of 100-500 nm, advantageously 200-400 nm. It may also be preferred that the particle size is very small, e.g. in the range of 2-150 nm, preferably 3-100 nm, advantageously 4-80 nm or e.g. 5-50 nm or e.g. 8-30 nm or e.g. 10-20 nm.
  • Very small particles e.g. with a particle size of in particular 2, 3, 4, 5 or 10 nm, can also form together agglomerates, which are then correspondingly larger, e.g. up to 600 nm or up to 500 nm or up to 400 nm or up to 300 nm in size, etc.
  • the particle size may advantageously be, for example, at values such as 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm or 60 nm.
  • very small particle sizes below 50 nm, below 40 nm, below 30 nm or below 20 nm may be preferred.
  • the particle size can then advantageously be, for example, at values such as 2 nm, 3 nm, 4 nm, 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm or 60 nm. Such values are preferred.
  • the bulk density of the preferably modified titanium dioxide is preferably in the range from 100 to 800 g / l, advantageously from 200 to 600 g / l, in particular from 300 to 500 g / l.
  • the bulk density may be 350 g / l, 400 g / l or 500 g / l.
  • the (preferably modified) titanium dioxide is present in the anatase crystal modification.
  • the modified titanium dioxide described above is characterized by a very good photocatalytic activity, in particular with the use of daylight.
  • visible to the human eye radiation of the visible region of the spectrum with wavelengths between 380 and 800 nm are used very well for the purposes of degradation, deactivation or reduction of impurities from the described modified titanium dioxide.
  • Even UV radiation between 10-380 nm can be used very well.
  • a particularly particularly preferred particle comprises a) photocatalytic material in amounts of 0.01-40% by weight, preferably 0.1-30% by weight, advantageously 1-20% by weight more preferably 5-15% by weight, in particular 8-12% by weight, of the carrier material, preferably comprising spray-dried powder, in particular comprising zeolite, in quantities of 30-90% by weight, preferably 40-80% by weight, advantageously 50-70% by weight, in particular 55-65% by weight c) organic solvent, preferably nonionic surfactant and / or humectant, in amounts of 5-60% by weight, preferably 10-50% by weight, advantageously 20% -40 wt .-%, in particular 25-35 wt .-%.
  • particles comprising a viscosifying agent according to the invention preferably comprise oils, cationic surfactants such as, in particular, esterquats, layered silicates, fatty acid derivatives, silicone oils, polymers, such as preferably silicone-based cationic surfactants or polyethylene-based polymers, preferably in an amount of 0.05 to 10 wt .-%, preferably 0.1 to 5 wt .-% by weight based on the total particles, a preferred embodiment of the invention is.
  • the avivage component includes, for example, quaternary ammonium compounds such as monoalk (en) yltrimethylammonium compounds, dialk (en) yldimethylammonium compounds, mono-, di- or triesters of fatty acids with alkanolamines.
  • Suitable examples of usable quaternary ammonium compounds are shown, for example, in the formulas (I) and (II): wherein in (I) R is an acyclic alkyl radical having 12 to 24 carbon atoms, R 1 is a saturated C 1 -C 4 alkyl or hydroxyalkyl radical, R 2 and R 3 are either R or R 1 or are an aromatic radical , X ⁇ represents either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these.
  • Examples of cationic compounds of the formula (I) are monotaltrimethylammonium chloride, monostearyltrimethylammonium chloride, didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.
  • R 4 is an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds and / or optionally with substituents
  • R 5 is H, OH or O (CO) R 7
  • R 6 is, independently of R 5, H, OH or O (CO) R 8
  • R 7 and R 8 are each independently an aliphatic alk (ene) ylrest having 12 to 22 carbon atoms with O, 1, 2 or 3 double bonds
  • m, n and p may each independently have the value 1, 2 or 3 have.
  • X can be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these anions.
  • R 5 represents the group 0 (CO) R 7 .
  • R 5 is the group 0 (CO) R 7 and R 4 and R 7 are alk (en) yl radicals having 16 to 18 carbon atoms.
  • R 6 is also OH.
  • Examples of compounds of the formula (I) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyloxyethyl) ammonium methosulfate, bis (palmitoyloxyethyl) hydroxyethyl methyl ammonium methosulfate, 1, 2-bis [tallowloxy] -3-trimethylammonium propane chloride or methyl N, N-bis (stearoyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulphate.
  • the acyl groups whose corresponding fatty acids have an iodine number between 1 and 100, preferably between 5 and 80, more preferably between 10 and 60 and in particular between 15 and 45, are preferred and having a cis / trans isomer ratio (in weight percent) of greater than 30:70, preferably greater than 50:50, and more preferably equal to or greater than 60:40.
  • Stepan under the tradename Stepantex ® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ® Cognis products, known under Rewoquat ® products from Degussa or those known under Tetranyl® products of Kao.
  • Further preferred compounds are the diester quats of the formula (III) which are obtainable under the name Rewoquat® W 222 LM or CR 3099.
  • R 21 and R 22 are each independently an aliphatic radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.
  • plasticizer compounds which have the following groups: RO (CO), N (CO) R or RN (CO), of which N (CO) R groups are preferred.
  • R 12, R 13 and R 14 independently represents a C- ⁇ _ 4 alkyl, alkenyl or hydroxyalkyl group
  • R 15 and R 16 are each independently selected a C. 8 28 -alkyl group
  • X ⁇ is an anion
  • r is a number between 0 and 5.
  • a preferred example of a cationic deposition aid according to formula (V) is 2,3-bis [tallowacyloxy] -3-trimethylammoniumpropane chloride.
  • plasticizing components which can be used according to the invention are quaternized protein hydrolyzates or protonated amines.
  • cationic polymers are also suitable softening component.
  • Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also referred to as Merquats.
  • polymers Polymer JR, LR and KG series of Amerchol
  • polyquaternium-4 copolymers such as graft copolymers having a cellulose backbone and quaternary ammonium groups bonded via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyltriammonium chloride, and similar quaternized guar Derivatives (eg Cosmedia Guar from Cognis or the Jaguar series from Rhodia), cationic quaternary sugar derivatives (cationic alkyl polyglucosides), eg the commercial product Glucquat® 100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 hydroxypropyl dimonium chlorides", copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers.
  • polyquaternized polymers eg Luviquat® Care from BASF
  • cationic biopolymers based on chitin and their derivatives, for example the polymer available under the trade name Chitosan® (manufacturer: Cognis).
  • Chitosan® manufactured under the trade name Chitosan® (manufacturer: Cognis).
  • Some of the cited cationic polymers additionally have skin and / or textile care properties.
  • R 17 can be an aliphatic alk (en) yl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds, s can assume values between 0 and 5.
  • R 18 and R 19 are un ⁇ each other for H, C- ⁇ _ 4 alkyl or hydroxyalkyl and X ⁇ is an anion.
  • softening components include protonated or quaternized polyamines.
  • plasticizing components are alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group.
  • alkylated quaternary ammonium compounds of which at least one alkyl chain is interrupted by an ester group and / or amido group.
  • Very particular preference is given to N-methyl-N- (2-hydroxyethyl) -N, N- (ditallowacyloxyethyl) ammonium methosulfate or bis (palmitoyloxyethyl) -hydroxyethyl-methylammonium methosulfate.
  • nonionic softening components such as especially polyoxyalkylene glycol alkanoates, polybutylenes, long chain fatty acids, ethoxylated fatty acid ethanolamides, alkyl polyglucosides, especially sorbitan mono, di- and triesters, and fatty acid esters of polycarboxylic acids
  • the most preferred optional use agents include cationic cellulose derivatives, cationic starches, copolymers of a diallyl quaternary ammonium salt and an acrylamide, quaternized vinylpyrrolidone vinylimidazole polymer polyglycolamine condensates, quaternized collagen polypeptides, polyethyleneimine, cationized silicon polymer (e.g., amodimethicone), cationic silicon polymers, e.g. provided in a mixture with other components under the trademark Dow Corning 929 (cationized emulsion), copolymers of adipic acid and
  • skin care agents or skin-care active substances are also present in the particles according to the invention, in particular in amounts
  • Skin care products may be in particular those agents which the
  • Skin care agents may e.g. Proteins, amino acids, lecithins, lipids, phosphatides,
  • Skin-care active substances are all those active substances which give the skin a sensory and / or cosmetic advantage.
  • Skin-care active substances are preferably selected from the following substances: a) waxes such as, for example, carnauba, spermaceti, beeswax, lanolin and / or derivatives thereof and others.
  • Hydrophobic plant extracts c) Hydrocarbons such as squalene and / or squalanes
  • Hydrocarbons such as squalene and / or squalanes
  • Higher fatty acids preferably those having at least 12 carbon atoms, for example lauric acid, stearic acid, behenic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, isostearic acid and / or polyunsaturated fatty acids and other.
  • Higher fatty alcohols preferably those having at least 12 carbon atoms, for example, lauryl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, cholesterol and / or 2-hexadecanol and others.
  • esters preferably such as cetyloctanoates, lauryl lactates, myristyl lactates, cetyl lactates, isopropyl myristates, myristyl myristates, isopropyl palmitates, isopropyl adipates, butyl stearates, decyl oleates, cholesterol stearates, glycerol monostearates, glycerol distearates, glycerol tristearates, alkyl lactates, alkyl citrates and / or alkyl tartrates and others.
  • lipids such as cholesterol, ceramides and / or sucrose esters and others.
  • vitamins such as vitamins A and E, vitamin C esters, including vitamin
  • Preferred skin care active ingredients are also essential oils, in particular selected from the group of Angelica fine - Angelica archangelica, Anis - Pimpinella anisum, Benzoin siam - Styrax tokinensis, Cabreuva - Myrocarpus fastig iatus, Cajeput - Melaleuca leucadendron, Cistrose
  • Cistrus ladaniferus Copaiba balm - Copaifera reticulata, Costus root - Saussurea discolor, Edeltann needle - Abies alba, Elemi - Canarium luzonicum, Fennel - Foeniculum dulce Spruce needle - Picea abies, Geranium - Pelargonium graveolens, Ho leaves - Cinnamonum camphora, Immortelle (Straw flower ) Helichrysum ang., Ginger extra - Zingiber off., St.
  • Preferred skin-care active ingredients are also skin-protecting oils, in particular selected from the group algae oil Oleum Phaeophyceae, aloe vera oil aloe vera brasiliana, apricot kernel oil Prunus armeniaca, arnica montana arnica, avocado oil Persea americana, borage oil Borago officinalis, calendula oil Calendula officinalis, camellia oil Camellia oleifera, thistle oil Carthamus tinctorius, Peanut oil Arachis hypogaea, Hemp oil Cannabis sativa, Hazelnut oil Corylus avellana, Hypericum perforatum, Jojoba oil Simondsia chinensis, Caraway oil Daucus carota, Cocos nucifera coconut oil, Pumpkin seed oil Curcubita pepo, Kukui nut oil Aleurites moluccana, Macadamia nut oil Macadamia ternifolia, Almond oil Pru
  • a particle according to the invention contains fragrances (perfume oil), preferably in amounts of 0.01 to 10 wt .-%, based on the total weight of particles.
  • fragrances perfume oil
  • the fragrances promote the consumer's acceptance of the product and convey a sense of cleanliness. Suitable fragrances are described below.
  • the particles according to the invention are powdered and / or surrounded by a coating, which preferably comprises thermoplastics such as PEG, PVA, polyacrylates, PVP, carbohydrates, polyesters such as preferably PET.
  • a coating which preferably comprises thermoplastics such as PEG, PVA, polyacrylates, PVP, carbohydrates, polyesters such as preferably PET.
  • Contain particles of the invention carrier material having an average particle size between 0.1 and 2.0 mm, preferably 0.15 and 1, 5 mm, in particular 0.2 and 1, 2 mm, so again there is a preferred embodiment of the invention.
  • Another object of the invention are granules comprising aggregates of several particles of the invention.
  • Such granules are obtainable by agglomeration of the particles according to the invention, for example in a mixer using conventional binders.
  • the aggregates may also contain other particles in addition to the particles according to the invention.
  • Another object of the invention is a washing or cleaning agent containing particles of the invention and / or granules.
  • particles, granules, detergents or cleaners according to the invention may comprise further optional ingredients, in particular washing, care and / or cleaning active ingredients, advantageously selected from the group comprising anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, acidifiers , Alkalizing agents, antibacterial agents, antioxidants, anti-redeposition agents, antistatics, builders, bleaches, bleach activators, bleach stabilizers, bleach catalysts, cobuilders, dispersants, electrolytes, enzymes, colorants, colorants, dyes, fluorescers, fungicides, germicides, odor-complexing agents, adjuvants, Hydrotropes, rinse aids, complexing agents, preservatives, corrosion inhibitors, optical brighteners, perfume carriers, pearlescers, pH Adjusting agents, repellents and impregnating agents, polymers, fragrance (s) (perfume (oil)), swelling and anti-slip agents, foam inhibitors,
  • the washing or cleaning agent according to the invention may be contained or packaged in an opaque packaging.
  • the opaque packaging allows for improved storage stability of the washing or cleaning agent according to the invention.
  • a preferred washing or cleaning agent according to the invention may, in addition to the particles and / or granules according to the invention, e.g. the following components (both individual components and all these components):
  • anionic surfactants preferably alkylbenzenesulfonates, alkanesulfonates, methyl ester sulfonates, ⁇ -olefinsulfonates, alkyl sulfates and / or alkyl ether sulfates, advantageously in amounts of 0-40 wt .-%, preferably in amounts of 1-25 wt .-%, in particular in amounts of 5-15% by weight
  • Nonionic surfactants preferably alkoxylated fatty alcohols, alkylphenol polyglycol ethers, alkoxylated fatty acid alkyl esters, polyhydroxy fatty acid amides, alkyl glycosides, alkyl polyglucosides, sucrose esters, sorbitan esters, amine oxides, fatty acid glucamides and / or the long-chain alkyl sulfoxides, advantageously in amounts of 0-20% by weight, preferably 0, 1-15% by weight, in particular 1-10% by weight,
  • (c) builders preferably zeolite, alkaline amorphous disilicates, crystalline layered silicates, polycarboxylate and / or sodium citrate, advantageously in amounts of 0-70% by weight, preferably 5-60% by weight, in particular 10-50% by weight,
  • alkalis preferably NaOH, KOH and / or sodium carbonate, advantageously in amounts of 0-30 wt .-%, preferably 1-25 wt .-%, in particular 5-15 wt .-%
  • bleaching agent preferably sodium perborate and / or sodium percarbonate, preferably in amounts of 0-25% by weight, in particular 5-20% by weight
  • corrosion inhibitors preferably sodium silicate, advantageously in amounts of 0-10% by weight, preferably 0.5-6% by weight, in particular 1-5% by weight,
  • (g) stabilizers preferably phosphonates, advantageously 0-5% by weight, in particular 0.01-1% by weight,
  • foam inhibitor preferably soap, silicone oils and / or paraffins, advantageously in amounts of 0-8 wt .-%, preferably 0.1-5 wt .-%, in particular 1-4 wt .-%
  • enzymes preferably proteases, amylases, mannanases, tannases, cellulases and / or lipases, advantageously in amounts of 0-5 wt .-%, preferably 0.1-5 wt .-%, in particular 0.5-2 wt .-%
  • grayness inhibitor preferably carboxymethyl cellulose, advantageously in amounts of
  • (k) discoloration inhibitor preferably polyvinylpyrrolidone derivatives, advantageously in amounts of 0-2% by weight, preferably 0.01-1.2% by weight, in particular 0.05-0.5% by weight,
  • (I) adjusting agent preferably sodium sulfate, advantageously in amounts of 0-50 wt .-%, preferably 5-40 wt .-%, in particular 10-30 wt .-%,
  • fragrances preferably in amounts of 0-10% by weight, in particular 0.01-5% by weight
  • optical brighteners preferably stilbene derivatives and / or biphenyl derivatives, advantageously in amounts of 0-3% by weight, preferably 0.01-1% by weight, in particular 0.005%
  • softening agents preferably oils, cationic surfactants, in particular esterquats, phyllosilicates,
  • Fatty acid derivatives silicone oils, polymers, such as preferably polymeric cationic surfactants
  • Silicone base or polymers based on polyethylene preferably in an amount of 0 to 15 wt .-%, advantageously 0.1 to 10 wt .-%, in particular 0.5 to 5 wt .-%,
  • (p) skin-care active substances preferably those as described above, preferably in an amount of 0 to 15% by weight, advantageously 0.1 to 10% by weight, in particular 0.5 to 5% by weight.
  • (q) water preferably in amounts of 0-30% by weight, preferably 0.1 to 20% by weight, in particular 1-15% by weight
  • (R) optionally salt replacement polymers preferably those as described below, in particular in amounts> 0.01 wt .-%.
  • the aforesaid components i. some of these, several or all of these, may also be part of the particles and / or granules according to the invention.
  • Suitable salt substitute polymers which are preferably used are, for example, the sulfonic acid-containing polymers which are used with particular preference.
  • sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, sulfonic acid-containing monomers and optionally other ionic or nonionic monomers.
  • R 1 to R 3 independently of one another are -H, -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or straight chain radical branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with - NH 2 , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR 4 , wherein R 4 is a saturated or unsaturated, straight-chain or branched Hydrocarbon radical having 1 to 12 carbon atoms.
  • Particularly preferred monomers containing sulfonic acid groups are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3 Methacrylamido-2-hydroxypropanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, Methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propenylsulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethacrylamide, sulfomethylmethacrylannicl and water-soluble salts of said acids.
  • Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds.
  • the content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer.
  • the copolymers may contain the monomers from groups i) and ii) and, if appropriate, iii) in varying amounts, it being possible for all representatives from group i) to be combined with all representatives from group ii) and all representatives from group iii).
  • Particularly preferred polymers have certain structural units, which are described below.
  • copolymers which are structural units of the formula are preferred.
  • These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative.
  • acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred.
  • the corresponding copolymers contain the structural units of the formula
  • Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
  • maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula
  • the sulfonic acid groups may be wholly or partially in neutralized form, i. the acidic acid of the sulfonic acid group in some or all sulfonic acid groups can be exchanged for metal ions, preferably alkali metal ions and in particular for sodium ions.
  • metal ions preferably alkali metal ions and in particular for sodium ions.
  • partially or fully neutralized sulfonic acid-containing copolymers is preferred according to the invention.
  • the monomer distribution of the copolymers preferably used according to the invention in the case of copolymers which contain only monomers from groups i) and ii) is preferably in each case from 5 to 95% by weight i) or ii), particularly preferably from 50 to 90% by weight monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
  • terpolymers particular preference is given to those containing from 20 to 85% by weight of monomer from group i), from 10 to 60% by weight of monomer from group ii) and from 5 to 30% by weight of monomer from group iii) ,
  • the molar mass of the sulfo copolymers which can preferably be used according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
  • Preferred washing or cleaning agents are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 15,000 gmol "1 .
  • the washing and / or cleaning agent according to the invention is present in portioned form, preferably in a pouch or as a tablet.
  • Another object of the invention is a process for preparing a particle according to the invention in which a suspension of photocatalytic material and an organic solvent is formed in a first step, and the resulting suspension is mixed in a second step with a solid support material.
  • the photocatalytic material is microfine dispersed in the suspension, in particular, the photocatalytic material contained is not visually recognizable as a solid.
  • the photocatalytic material to be used and the organic solvent are preferably those already described above.
  • the organic solvent thus preferably contains nonionic surfactants and / or humectants.
  • the solid support material to be used is preferably that which has already been described above, ie preferably comprises inorganic material, in particular zeolite, sulfate, carbonate, silicate, clay, silica and / or mixtures thereof, in particular spray-dried material.
  • the weight ratio of the photocatalytic material to organic solvent in the prepared suspension may preferably be in the range of 1: 1 to 1:40, advantageously 2: 3 to 1: 30, more preferably in the range of 1: 2 to 1:20.
  • weight ratios of the photocatalytic material to organic solvent in the range from 1: 2 to 1:15, for example 1: 2 to 1:10 or 1: 2 to 1: 5 can be very advantageous.
  • a weight ratio of photocatalytic material to organic solvent of 1: 3 is very advantageous. It is particularly advantageous if> 50% by weight, preferably> 60% by weight, in particular> 70% by weight, of the total suspension consists of nonionic surfactant.
  • suspension with the solid support material may advantageously 40 to 90 wt .-%, preferably 50 to 80 wt .-%, in particular 60-70 wt .-% of solid support material with advantageously 10 to 60 wt .-%, preferably 20-50, in particular 30-40 wt .-% are reacted to suspension, wt .-% based on the total weight of suspension and solid support material.
  • the particles to be produced contain other ingredients, they can be incorporated in various ways.
  • solids and liquids may be included in the above suspension before being mixed in a second step with a solid support material.
  • solids and liquids may be added when the suspension is mixed with a solid carrier material.
  • suitable solids and liquids may also be incorporated into the solid support material before it is mixed with said suspension.
  • the particles obtained are converted in a further step by granulation in a mixer using a binder in coarser granules. It is also possible to agglomerate the particles not only with themselves, but also with other particles. Advantageously, other agglomeration methods are also applicable, e.g. Fluidized bed process.
  • Suitable granulation liquids may be, for example, aqueous solutions of polymers or of sticky substances, for example glucose.
  • Aqueous granulation liquids may contain, for example, salts, waterglass, alkylpolyglycosides, carbohydrates (saccharides), natural and / or synthetic polymers, in particular cellulose ethers, polyacrylates, starch, PEG, PVAL and / or biopolymers, for example xanthan.
  • As granulation liquids and water-poor systems can be used, for example based on organic solvents containing swollen polymers. It is also possible to use anhydrous granulation liquids, for example melts or dihydric or polyhydric alcohols.
  • multiphase granulation liquids for example aqueous systems, for example based on an oil-polymer-water emulsion, based on a surfactant mixture with air or based on a system of nonionic surfactant and polymer solution.
  • anhydrous systems are used, namely, for example, solids-containing melts, or systems of polymer and solvent.
  • the granulation aid may comprise solubilizer (hydrotrope).
  • solubilizer hydrotropes are e.g. Xylene or cumene sulphonate or other substances, e.g. Urea or N-methylacetamide.
  • Granulation foams are also particularly suitable.
  • a granulation foam is obtained, for example, by applying a gaseous medium to a flowable component and thus foaming it up.
  • a granulation foam is, for example, a surfactant foam which has been obtained by foaming a flowable, surfactant-containing component with a gaseous medium and can be used as a granulation aid.
  • the granulation foam preferably has mean pore sizes below 10 mm, preferably below 5 mm and in particular below 2 mm. By using a granulation foam instead of conventional granulating liquids even more homogeneous liquid distributions can be achieved during the granulation process. It is preferred if at least one granulation foam and at least one granulation liquid are used in the granulation. The particles to be granulated can be wetted even better when granulation foam is used.
  • the resulting granules may have a bulk density in the range of 200-1500 g / l.
  • the lower limit for the bulk density may also be at a value of preferably 250, 300, 350, 400, 450, 500, 550, 600, 650, 700 or even 750 g / L. It is also possible that the lower limit is even higher, e.g. at 800g / L.
  • the upper limit for the bulk density may be at a value of preferably 1450, 1400, 1350, 1300, 1250, 1200, 1150, 1100, 1050, 1000, 950, 900, 850, 800 or 750 g / L. It is also possible that the upper limit is even lower, e.g. at a value of preferably 700, 650, 600, 550 or 500 g / L.
  • Another object of the invention is a process for the preparation of a powdered detergent or cleaning agent, wherein in a first step inventive particles or granules are provided, and are mixed in a further step with a powder detergent or cleaning agent matrix.
  • Another object of the invention is a method for cleaning hard surfaces, in particular crockery, by treating these hard surfaces with a cleaning liquid containing particles according to the invention, granules and / or washing or cleaning agent after, at and / or followed by exposure of the hard surface to light in the wavelength range of 10-1200 nm.
  • Cleaning fluid containing particles according to the invention, granules and / or detergents or cleaners means that the particles, granules and / or or washing or cleaning agents are dissolved in a liquid, preferably water.
  • the above method is performed using an automatic dishwashing machine, preferably an automatic dishwashing machine with a light source.
  • Another object of the invention is a method for applying fine particulate photocatalytic material to textiles by treating these textiles in a textile treatment bath, to which particles according to the invention, granules or detergents or cleaning agents.
  • Another object of the invention is a process for cleaning, care, equipment, finishing and / or conditioning of textiles by treatment of these textiles in a textile treatment bath to which particles of the invention, granules or detergents or cleaners are added, and / or followed by exposure of the textile article to light in the wavelength range of 10-1200 nm.
  • the method according to the invention for the prophylaxis treatment of textiles in the form of an anticipatory defense and inhibition of stains and stains on the textile using light in the wavelength range of 10-1200 nm, so is also a preferred embodiment of the invention.
  • a dirt-repellent equipment i. Stains should be prevented or made more difficult or the staining of textiles is made more difficult.
  • a preferred embodiment of the invention is provided.
  • the method of the present invention is to remove, alleviate or reduce stains and stains on fabrics derived from: red to blue anthocyanin dyes, e.g. Cyanidin, e.g. from cherries or blueberries, red betanidine from beetroot, orange-red carotenoids, e.g. Lycopene, beta-carotene, e.g. from tomatoes or carrots, yellow curcuma dyes, e.g. Curcumin, e.g. curry and mustard, brown tannins, e.g. from tea, fruit, red wine, deep brown humic acid, e.g. from coffee, tea, cocoa, green chlorophyll, for example, from green grasses, technical dyes from cosmetics, inks, colored pencils
  • red to blue anthocyanin dyes e.g. Cyanidin, e.g. from cherries or blueberries, red betanidine from beetroot, orange-red carotenoids, e.g. Lycopene, beta
  • a method according to the invention which is a manual process carried out in an open tub or bowl or similar container, in particular hand washing, prewashing and / or soaking, the tub being treated with the wash liquor after the textiles to be treated penetrates light in the wavelength range of 10-1200 nm, in particular sunlight, preferably for a period of> 5 minutes, represents a further preferred embodiment of the invention.
  • Another object of the invention is the use of particles of the invention, granules and detergents or cleaning agents in textile treatment, especially textile laundry, to facilitate the removability of dirt, preferably colored dirt (colored spots) of textiles, using light in the wavelength range of 10 -1200 nm, by equipping the textiles with photocatalytic material.
  • Another object of the invention is the use of particles of the invention, granules and detergents or cleaning agents in textile treatment, especially textile laundry, to hinder the Beschmutzles of textiles, in particular the Beschmutzbarkeit with colored spots, using light in the wavelength range of 10 to 1200 nm , by equipping the textiles with photocatalytic material.
  • Another object of the invention is the use of particles of the invention, granules and detergents or cleaning agents in the textile treatment to reduce the fiber adhesion of dirt, preferably colored dirt (colored spots) on textiles, using light in the wavelength range of 10-1200 nm, by finishing the textiles with photocatalytic material.
  • Another object of the invention is the use of particles according to the invention, granules and detergents or cleaners in textile treatment to increase the water solubility of dirt, preferably colored dirt (colored stains) on textiles, using light in the wavelength range of 10-1200 nm, by equipping the textiles with photocatalytic material.
  • Another object of the invention is the use of particles of the invention, granules and detergents or cleaning agents in the textile treatment to prevent the formation of fetid odors on the textiles, using light in the wavelength range of 10-1200 nm, by equipping the textiles with photocatalytic material ,
  • Another object of the invention is the use of particles of the invention, granules and detergents or cleaning agents in the textile treatment for equipping the
  • Textiles with a self-cleaning power using light in the wavelength range of 10-1200 nm, by finishing the textiles with photocatalytic material.
  • light in the wavelength range of 10-380 nm and / or 380-800 nm is preferred.
  • Anionic surfactants may preferably be present in the agents according to the invention.
  • anionic surfactants for example, those of the sulfonate type and sulfates are used.
  • surfactants of the sulfonate type preferably come here C 9 .i 3 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as they are, for example, from C 12 -i 8 monoolefins with terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.
  • alkanesulfonates which are obtained from C 12 -i 8 -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids for example, the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or Taigfettcicren are suitable.
  • sulfated fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as in the preparation by esterification of a monoglycerol with 1 to 3 mol of fatty acid or in the conversion of esterification of triglycerides with 0.3 to 2 moles of glycerol.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelhoffreschester C 2 -C 8 fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or d 0 -C 2 o Oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
  • Ci 2 -Ci 6 alkyl sulfates and Ci 2 -Ci 5 alkyl sulfates and Ci 4 -Ci 5 alkyl sulfates are preferred.
  • 2,3-Alkyl sulfates can be obtained under the name DAN ® as commercial products from Shell Oil Company, are suitable anionic surfactants.
  • 2 i-alcohols such as 2-methyl-branched C 9 .n-alcohols having on average 3.5 moles of ethylene oxide (EO) or Ci 2 -i 8 -fatty alcohols having 1 to 4 EO, are suitable. Due to their high foaming behavior, they are preferably used only in relatively small amounts, in particular in cleaning agents.
  • the agents according to the invention may preferably be free of sulfuric acid monoester.
  • Suitable anionic surfactants are, for example, the partial esters of di- or polyhydroxyalkanes, mono- and disaccharides, polyethylene glycols with the EO adducts of maleic anhydride to at least monounsaturated carboxylic acids having a chain length of 10 to 25 carbon atoms with an acid number of 10 to 140.
  • preferred anionic surfactants have 4 to 28, preferably 6 to 20, in particular 8 to 18, particularly preferably 10 to 16, most preferably 12 to 14 carbon atoms, two or more anionic, in particular two, acid groups, preferably carboxylate, sulfonate and / or sulfate groups, in particular a carboxylate and a sulfate group on.
  • Examples of these compounds are the alpha sulfo fatty acid salts, the acyl glutamates, the monoglyceride disulfates, and the alkyl ethers of the glycerol disulfate, and in particular the monoester sulfosuccinates described below.
  • Particularly preferred anionic surfactants are the sulfosuccinates, sulfosuccinamates and sulfosuccinamides, especially sulfosuccinates and sulfosuccinamates, most preferably sulfosuccinates.
  • the sulfosuccinates are the salts of the mono- and di-esters of sulfosuccinic acid HOOCCH (SO 3 H) CH 2 COOH, while the sulfosuccinamates mean the salts of the monoamides of sulfosuccinic acid and the sulfosuccinamides the salts of diamides of sulfosuccinic acid ,
  • the salts are preferably alkali metal salts, ammonium salts and mono-, di- or trialkanolammonium salts, for example mono-, di- or triethanolammonium salts, in particular lithium, sodium, potassium or ammonium salts, particularly preferably sodium or ammonium salts preferably sodium salts.
  • one or both carboxyl groups of the sulfosuccinic acid is preferably with one or two identical or different unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alcohols having 4 to 22, preferably 6 to 20, in particular 8 to 18 , more preferably 10 to 16, most preferably 12 to 14 carbon atoms esterified.
  • esters of unbranched and / or saturated and / or acyclic and / or alkoxylated alcohols in particular unbranched, saturated fatty alcohols and / or unbranched, saturated, with ethylene and / or propylene oxide, preferably ethylene oxide, alkoxylated fatty alcohols having a degree of alkoxylation of 1 to 20, preferably 1 to 15, in particular 1 to 10, more preferably 1 to 6, most preferably 1 to 4.
  • the monoesters are preferred in the context of the present invention over the diesters.
  • a particularly preferred sulfosuccinate is Sulfobernsteinklarylpolyglykolester-di-sodium salt (lauryl EO sulfosuccinate, di-sodium salt; INCI Disodium Laureth Sulfosuccinate), for example, as Tego ® sulfosuccinate F 30 (Goldschmidt) with a sulfosuccinate of 30 parts by weight % is commercially available.
  • one or both form carboxyl groups of the sulfosuccinic acid preferably with a primary or secondary amine having one or two identical or different, unbranched or branched, saturated or unsaturated, acyclic or cyclic, optionally alkoxylated alkyl radicals having 4 to 22 , preferably 6 to 20, in particular 8 to 18, more preferably 10 to 16, most preferably 12 to 14 carbon atoms carries, a carboxylic acid amide.
  • Particular preference is given to unbranched and / or saturated and / or acyclic alkyl radicals, in particular unbranched, saturated fatty alkyl radicals.
  • sulfosuccinates and sulfosuccinamates designated according to INCI: ammonium dinonyl sulfosuccinates, ammonium lauryl sulfosuccinates, diammonium dimethicone copolyol sulfosuccinates, diammonium lauramido-MEA sulfosuccinates, diammonium lauryl sulfosuccinates, diammonium oleamido PEG-2 Sulfosuccinate, Diamyl Sodium Sulfosuccinate, Dicapryl Sodium Sulfosuccinate, Dicyclohexyl Sodium Sulfosuccinate, Diheptyl Sodium Sulfosuccinate, Dihexyl Sodium Sulfosuccinate, Diisobutyl Sodium Sulfosuccinate, Dioctyl Sodium Sulfosuccinate, Dioctyl
  • Another suitable class of compounds are anionic surfactant-cation complexes, the cation itself initially having surfactant properties.
  • Examples are transesterification products of LAS acid with amines, amine derivatives, containing a C chain with> 2 C atoms, preferably C 12 -C 16 . These can be oxidized, for example, on the nitrogen, ie for example transesterification of LAS acid with amine oxide C12-14.
  • an inventive washing or cleaning agent to anionic surfactants can vary within wide ranges.
  • a washing or cleaning agent according to the invention may contain very large amounts of anionic surfactant, preferably up to an order of magnitude of up to 40, 50 or 60% by weight or more, based on the total washing or cleaning agent.
  • a washing or cleaning agent according to the invention may contain only very small amounts of anionic surfactant, for example less than 15 or 10% by weight or less than 5% by weight or even less.
  • anionic surfactants are advantageously present in amounts of from 0.1 to 40% by weight and in particular from 5 to 30% by weight, with concentrations above 10% by weight and even above 15% by weight.
  • the washing or cleaning agent according to the invention comprises anionic surfactants, preferably in amounts of at least 0.01% by weight, based on the total washing or cleaning agent.
  • the washing or cleaning agent according to the invention may be free of anionic surfactant.
  • the particles according to the invention and also granules can be free from anionic surfactant.
  • soaps may be present in the compositions according to the invention, in particular in the detergents or cleaners.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the content of a preferred washing or cleaning agent according to the invention on soaps is, independently of other anionic surfactants, preferably not more than 3% by weight and in particular from 0.5 to 2.5% by weight, based on the total washing or cleaning agent ,
  • the agent of the invention is soap.
  • the anionic surfactants and soaps may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • they are in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • nonionic surfactants may be included in the compositions of the invention.
  • their content in detergents or cleaners according to the invention can be up to 2 or 3 or 5% by weight, based on the total washing or cleaning agent.
  • Larger amounts of nonionic surfactant may also be included in the washing or cleaning agent, for example up to 5% by weight or 10% by weight or 15% by weight or 20% by weight, 30% by weight, 40% % By weight, 50% by weight or even more, if appropriate.
  • Sensible lower limits may be values of 0.01, 0.1, 1, 2, 3 or 4 wt .-%, wt .-% in each case based on the total detergent or cleaning agent
  • the nonionic surfactants are in relatively large amounts, ie up to 50% by weight, advantageously from 0.1 to 40% by weight, particularly preferably from 0.5 to 30 and in particular from 2 to 25% by weight, in each case based on the total washing or cleaning agent.
  • the washing or cleaning agent according to the invention contains nonionic surfactants, preferably in amounts of at least 0.1% by weight, based on the total washing or cleaning agent.
  • the washing or cleaning agent according to the invention may also be free of nonionic surfactant.
  • nonionic surfactants may be included in the inventive compositions.
  • the agents according to the invention may preferably also contain cationic surfactants.
  • Suitable cationic surfactants are, for example, surface-active quaternary compounds, in particular having an ammonium, sulfonium, phosphonium, iodonium or arsonium group.
  • Particularly preferred cationic surfactants are the quaternary, partially antimicrobial ammonium compounds (QAV, INCI Quaternary Ammonium Compounds) according to the general formula (R ') (R ") (R'") (R IV ) N + X " , in which R 1 to R ⁇ v identical or different CWAlkylreste 1 C 7 - 28 - aralkyl radicals or heterocyclic radicals, wherein two or in the case of an aromatic involvement as in pyridine even three radicals together with the nitrogen atom, the heterocycle, for example a pyridinium or imidazolinium compound, and X "are halide ions, sulfate ions, hydroxide ions or similar anions.
  • at least one of the radicals has a chain length of 8 to 18, in particular 12 to 16, carbon atoms.
  • QACs are prepared by reacting tertiary amines with alkylating agents, such as methyl chloride, Benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylating agents such as methyl chloride, Benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide produced.
  • alkylation of tertiary amines with a long alkyl radical and two methyl groups is particularly easy, the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions.
  • Amines having three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are preferably quaternized with dimethyl sulfate.
  • Suitable QACs are, for example, benzalkonium chloride (N-alkyl-N, N-dimethylbenzylammonium chloride, CAS No. 8001-54-5), benzalkone B (mp-dichlorobenzyl-dimethyl-C 1-4 -alkylammonium chloride, CAS No. 58390-78 -6), benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) -ammonium chloride), cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide, CAS No.
  • benzetonium chloride N , N-dimethyl-N- [2- [2- [p- (1,1,3,3-tetramethylbutyl) phenoxy] ethoxy] ethyl] benzylammonium chloride, CAS No. 121-54-0
  • dialkyldimethylammonium chlorides as Di-n-decyldimethylammonium chloride (CAS No. 7173-51-5-5), didecyldimethylammonium bromide (CAS No. 2390-68-3), dioctyldimethylammoniumchloric, 1-cetylpyridiniumchloride (CAS No.
  • Preferred QUATS are the benzalkonium chlorides containing C 8 -C 18 alkyl radicals, in particular C 2 -C 14 -Aklyl-benzyl-dimethylammonium niumchlorid.
  • a particularly preferred QAC Kokospentaethoxymethylammoniummethosulfat (INCI PEG-5 Cocomonium Methosulfate; Rewoquat CPEM ®).
  • anionic surfactants In order to avoid possible incompatibilities of any antimicrobial cationic surfactants to be used with anionic surfactants which may be present, it is possible to use e.g. as anionic surfactant compatible and / or possibly as little cationic surfactant used or omitted in a particular embodiment of the invention entirely on cationic surfactants.
  • the washing or cleaning agents according to the invention may comprise one or more cationic surfactants, advantageously in amounts, based on the total washing or cleaning agent, of from 0 to 30% by weight, more preferably greater than 0 to 20% by weight, preferably 0, 01 to 10 wt .-%, in particular 0.1 to 5 wt .-%. Suitable minimum values may also be 0.5, 1, 2 or 3 wt .-%.
  • the washing or cleaning agent according to the invention comprises cationic surfactants, preferably in amounts of at least 0.1% by weight, based on the total washing or cleaning agent.
  • the agent according to the invention preferably detergent or cleaning agent, can be free of cationic surfactant.
  • the agents according to the invention may also contain amphoteric surfactants. These will be described in more detail below.
  • the detergents or cleaners according to the invention may contain one or more amphoteric surfactants, advantageously in quantities, based on the total washing or cleaning agent Cleaning agent, from 0 to 30 wt .-%, more preferably greater than 0 to 20 wt .-%, preferably 0.01 to 10 wt .-%, in particular 0.1 to 5 wt .-%.
  • the agent of the invention may be free of amphoteric surfactants.
  • the washing or cleaning agents according to the invention may contain only very little total surfactant, e.g. the total amount of surfactant may be less than 20% by weight, 15% by weight, 10% by weight or 5% by weight, advantageously even less than 3% by weight or less than 1% by weight, in particular even less than 0.5 Wt .-% or less than 0.1 wt .-%, wt .-% in each case based on the total washing or cleaning agent.
  • the total surfactant content is preferably at least 0.01% by weight, 0.1% by weight or 1% by weight, based on the total washing or cleaning agent.
  • ingredients of the compositions of the invention may be inorganic and organic builders.
  • Inorganic builders include water-insoluble or non-water-soluble ingredients such as aluminosilicates and especially zeolites.
  • the agent according to the invention preferably detergent or cleaning agent
  • the agent contains zeolite. It may then be preferred that this zeolite content, based on the total weight of the washing or cleaning agent, less than 5 wt .-%, preferably at most 4 wt .-%, at most 3 wt .-% or at most 2 wt .-% is ,
  • the washing or cleaning agent according to the invention has a zeolite content of at least 10% by weight, e.g. at least 15 wt .-% or at least 20 wt .-% or at least 30 wt .-% or even beyond, for example, at least 50 wt .-%, wt .-% based on the total washing or cleaning agent
  • Soluble builders may be the washing or cleaning agent according to the invention, preferably in amounts of from 0.1% by weight to 30% by weight, preferably from 5% by weight to 25% by weight and particularly preferably from 10% by weight to 20 Wt .-%, based on the total weight of the washing or cleaning agent, with sodium carbonate is particularly preferred as a soluble builder.
  • the washing or cleaning agent according to the invention contains less than 10% by weight, for example less than 5% by weight, of soluble builder, based on the total washing or cleaning agent.
  • the washing or cleaning agent according to the invention may be free of soluble builder.
  • Useful finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP (R) (commercial product of Crosfield) is particularly preferred.
  • zeolite X and mixtures of A, X and / or P are particularly preferred.
  • zeolite A and zeolite X which as VEGOBOND AX ® (a product of Condea Augusta SpA) Trade is available.
  • VEGOBOND AX ® a product of Condea Augusta SpA
  • the zeolite can be used as a spray-dried powder or else as undried, still moist, stabilized suspension of its preparation.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated Ci 2 -Ci 8 -FeK- alcohols with 2 to 5 ethylene oxide groups, Ci 2 -Ci 4 fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of preferably less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • zeolites are faujasite-type zeolites. Together with the zeolites X and Y, the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which are characterized by the double-six-membered subunit D6R. In addition to the faujasite types mentioned, the zeolite structural group 4 also includes the minerals chabazite and gmelinite as well as the synthetic zeolites R (chabazite type), S (gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogs.
  • Faujasite-type zeolites are composed of ⁇ -cages linked by tetrahedral D6R subunits, with the ⁇ -cages resembling the carbon atoms in the diamond.
  • the three-dimensional network of the faujasite-type zeolites suitable according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities of about 13 A diameter and can be represented by the formula Na 86 [(AIO 2 ) 86 (SiO 2 ) i06] 264 H 2 O.
  • the network of zeolite X contains a void volume of about 50%, based on the dehydrated crystal, which represents the largest void space of all known zeolites (zeolite Y: about 48% void volume, faujasite: about 47% void volume).
  • zeolite type zeolite preferably denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
  • zeolite X zeolite Y and faujasite and mixtures of these compounds are also suitable according to the invention, with pure zeolite X being preferred.
  • Mixtures or cocrystallizates of faujasite-type zeolites with other zeolites, which need not necessarily belong to the zeolite structure group 4, are also suitable according to the invention, with preferably at least 50% by weight of the faujasite-type zeolites being suitable.
  • the suitable aluminum silicates are commercially available and the methods for their preparation are described in standard monographs.
  • zeolite A-LSX which corresponds to a cocrystal of zeolite X and zeolite A and in its anhydrous form has the formula (M 2 / n O + M'2 / n O) Al 2 O 3 zSiO 2 , wherein M and M 'may be alkali or alkaline earth metals and z is a number from 2.1 to 2.6.
  • VEGOBOND AX by the company CONDEA Augusta SpA
  • Y-type zeolites are also commercially available and can be obtained, for example, by the formulas
  • the particle sizes of the suitable zeolites are advantageously in the range from 0.1 ⁇ m to 100 ⁇ m, preferably from 0.5 ⁇ m to 50 ⁇ m and in particular from 1 ⁇ m to 30 ⁇ m, in each case measured by standard particle size determination methods.
  • the washing or cleaning agent of the invention may be free of zeolite.
  • all of the inorganic constituents contained should preferably be water-soluble. Therefore, builders other than the zeolites mentioned are used in these embodiments.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are selected from dialdehydes such as glyoxal, Glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Ethylenediamine-N, N '-di- succinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • EDDS Ethylenediamine-N, N '-di- succinate
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are, for example, 3 to 15 wt .-%, based on the total detergent or cleaning agent.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs.
  • EDTMP hexasodium salt of EDTMP
  • hepta- and octa-sodium salt of DTPMP hepta- and octa-sodium salt of DTPMP.
  • Builder is used from the class of phosphonates preferably HEDP.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, it may be preferable to use Aminoalkanphosphonate, in particular DTPMP, or to use mixtures of said phosphonates.
  • phosphates in particular pentasodium triphosphate, if appropriate also pyrophosphates and orthophosphates, which act primarily as precipitants for calcium salts.
  • Phosphates are predominantly used in automatic dishwasher detergents, but in some cases also in detergents.
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as dihydrate (density 1, 91 like “3 , melting point 60 °) and as monohydrate (density 2.04 like “ 3 ). Both salts are white powders which are very slightly soluble in water and which lose the water of crystallization when heated and at 200 ° C. into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33, like '3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) J and is readily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 like “3 , water loss at 95 °), 7 moles (density 1, 68 like “ 3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water (density 1, 52 "3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7.
  • Disodium hydrogen phosphate is used by neutralization of phosphoric acid with sodium carbonate solution
  • Di-potassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction Heating of Thomas slag with coal and potassium sulphate Despite the higher price, in the detergent industry the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 like “3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like '3 , melting point 94 ° Both substances are colorless crystals which are soluble in water with an alkaline reaction Na 4 P 2 O 7 is formed on heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dehydrating the solution by spraying.
  • Kali diphosphate potassium pyrophosphate
  • K 4 P 2 O 7 exists in the form of the trihydrate and is a colorless hygroscopic powder with a density of 2.33 "3 which is soluble in water, wherein the pH of the 1% solution at 25 ° is 10.4.
  • Condensation of the NaH 2 PO 4 or the KH 2 PO 4 results in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates.
  • cyclic representatives the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates.
  • hot or cold phosphates Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with soda solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate) is, for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two are used according to the invention exactly as sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; It is also possible to use mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate according to the invention.
  • carbonates and silicates are used as inorganic builder substances.
  • Formula NaMSi x O 2x + 1 yH 2 O where M is sodium or hydrogen, x is a number from 1.6 to 4, preferably 1.9 to 4.0 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
  • crystalline silicates are preferably subsequently added.
  • Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates
  • Na 2 Si 2 O 5 yH 2 O is preferred.
  • Such compounds are commercially available, for example, under the name SKS® (from Clariant).
  • SKS-6 ® is predominantly a ⁇ -
  • Sodium disilicate Kanemit NaHSi 2 O 5 yH 2 O commercially available under the names SKS-9 ® and SKS-10 ® (Clariant). It may also be advantageous to use chemical modifications of these phyllosilicates.
  • the alkalinity of the layered silicates can be suitably influenced.
  • Phyllosilicates doped with phosphate or carbonate have, compared to the ⁇ -sodium disilicate, altered crystal morphologies, dissolve more rapidly and show an increased calcium binding capacity in comparison to ⁇ -sodium disilicate.
  • phyllosilicates of the general empirical formula x Na 2 O • y SiO 2 • z P 2 O 5 in which the ratio x to y is a number 0.35 to 0.6, the ratio x to z a number of 1.75 to 1200 and the ratio y to z of a number of 4 to 2800 is known.
  • the solubility of the layered silicates can also be increased by using particularly finely divided layered silicates.
  • compounds from the crystalline layer silicates with other ingredients can be used.
  • compounds with Cellulosederivaten having advantages in the disintegrating effect, as well as compounds with polycarboxylates, such as citric acid, or polymeric polycarboxylates, such as copolymers of acrylic acid to call.
  • the preferred builder substances also include amorphous sodium silicates having a modulus Na 2 O: SiO 2 VOn of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which have secondary washing properties.
  • amorphous is also understood to mean "X-ray amorphous”. This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle.
  • the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which likewise have a dissolution delay compared with the conventional water glasses, are known.
  • Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
  • Particularly preferred inorganic water-soluble builders are alkali metal carbonates and alkali metal bicarbonates, with sodium and potassium carbonate, and especially sodium carbonate, being among the preferred embodiments.
  • Useful organic builders are, for example, usable in the form of their alkali and especially sodium polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for environmental reasons, as well as Mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof. The acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus, for example in the granules according to the invention, also serve to establish a lower and milder pH of detergents or cleaners.
  • an acidifying component for example in the granules according to the invention, also serve to establish a lower and milder pH of detergents or cleaners.
  • citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.
  • polymeric polycarboxylates for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular mass of 500 to 70,000 g / mol.
  • the molecular weights indicated are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated.
  • the agents of the invention may also contain polymers.
  • Suitable polymers which can also be used as carriers in conjunction with perfume include, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the content of detergents or cleaning agents on organic builders may vary within a wide range. Levels of from 2 to 20% by weight, in particular contents of not more than 10% by weight, are particularly preferred, based on the total washing or cleaning agent. According to another preferred embodiment, the agent according to the invention can be free from organic builders.
  • compositions according to the invention may contain components from the classes of the grayness inhibitors (soil carriers), the neutral salts and / or the fabric-softening auxiliaries (for example cationic surfactants), which is preferred.
  • Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble, acidic groups containing polyamides are for suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of preferably from 0.1 to 5% by weight. %, based on the total washing or cleaning agent used.
  • a typical example of a suitable representative of neutral salts is sodium sulfate. It can be used in amounts of, for example, from 0 to 60% by weight, preferably from 2 to 45% by weight, based on the total washing or cleaning agent.
  • the agents according to the invention may contain softening agents, e.g. Plasticizers.
  • Suitable lubricants are z.T. already described in more detail.
  • Suitable softening agents are, for example, also swellable phyllosilicates of the type of corresponding montmorillonites, for example bentonite, as well as cationic surfactants.
  • nonionic surfactants are described in more detail.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture may contain, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, palm kernel, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • the preferred ethoxylated alcohols include, for example, C 2 -C 4 -alcohols with 3 EO to 6 EO, C 9 -C-, i-alcohols with 7 EO, C 3 -C 5 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci 4 -Ci 5 -AlkO- hole with 4 EO, 5 EO, 7 EO or 9 EO, Ci 2 -Ci 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 2 -C 4 alcohol containing 3 EO and C 2 -C 8 alcohol containing 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • Preferred nonionic surfactants are one or more polyols with ethylene oxide (EO) and / or propylene oxide (PO) alkoxylated, branched or unbranched, saturated or unsaturated C 10 - 22 alcohols with a degree of alkoxylation up to 30, preferably ethoxylated C 10-i 8 - Fatty alcohols having a degree of ethoxylation of less than 30, preferably 1 to 20, in particular 1 to 12, especially preferably 1 to 8, more preferably 2 to 5, for example C
  • EO ethylene oxide
  • PO propylene oxide
  • nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number from 1 to 10; preferably x is 1, 1 to 1, 4. also suitable are N-methylglucamides with C 12 / C 14 .
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, particularly preferred are Ci 2 -Ci 8 -Fettkladester having an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are for example also used.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • alkoxylated amines advantageously ethoxylated and / or propoxylated, in particular primary and secondary amines having preferably 1 to 18 carbon atoms per alkyl chain and an average of 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per Mole of amine.
  • EO ethylene oxide
  • PO propylene oxide
  • compositions according to the invention which are particularly suitable for automatic dishwashing, in particular dishwashing compositions in the form of tablet tablets, such as tabs, all surfactants are suitable in principle as surfactants.
  • the nonionic surfactants described above and especially the low-foaming nonionic surfactants are particularly preferred for this purpose.
  • Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols.
  • n moles of ethylene oxide and one mole of alcohol form a complex mixture of addition products of different degrees of ethoxylation.
  • a further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
  • the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention.
  • Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.
  • compositions according to the invention may also contain foam inhibitors, for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • foam inhibitors for example foam-inhibiting paraffin oil or foam-inhibiting silicone oil, for example dimethylpolysiloxane.
  • suitable foam-inhibiting paraffin oils which may also be present in admixture with paraffin waxes, are generally complex mixtures without a sharp melting point.
  • the melting range is usually determined by differential thermal analysis (DTA) and / or the solidification point. This is the temperature at which the paraffin passes from the liquid to the solid state by slow cooling.
  • DTA differential thermal analysis
  • Paraffins with less than 17 carbon atoms are not useful in the invention, their proportion in the paraffin oil mixture should therefore be as low as possible and is preferably below the limit significantly measurable by conventional analytical methods, for example gas chromatography.
  • paraffins are used, which solidify in the range of 2O 0 C to 7O 0 C.
  • paraffin wax mixtures may contain different proportions of liquid paraffin oils.
  • the liquid fraction at 4O 0 C is as high as possible, even without being 100% at this temperature.
  • Preferred paraffin wax mixtures have at 4O 0 C a liquid content of at least 50% by weight, in particular from 55 wt .-% to 80 wt .-%, and at 6O 0 C, a liquid content of at least 90 wt .-%. This has the consequence that the paraffins, preferably down to at least 6O 0 C are flowable and pumpable at temperatures down to at least 7O 0 C.
  • paraffins contain as far as possible no volatile components.
  • Preferred paraffin waxes contain less than 1 wt .-%, in particular less than 0.5 wt .-% at 11O 0 C and atmospheric pressure vaporizable fractions.
  • Paraffins which can be used according to the invention can be obtained, for example, under the trade names Lunaflex® from Guer and Deawax® of DEA Mineralöl AG.
  • the paraffin oils may contain at room temperature solid bisamides derived from saturated fatty acids containing 12 to 22, preferably 14 to 18, carbon atoms and alkylenediamines having 2 to 7 carbon atoms.
  • Suitable fatty acids are lauric, myristic, stearic, arachic and behenic acid and mixtures thereof, such as those obtainable from natural fats or hardened oils, such as tallow or hydrogenated palm oil.
  • suitable diamines are ethylenediamine 1, 3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, p-phenylenediamine and toluenediamine.
  • Preferred diamines are ethylenediamine and hexamethylenediamine.
  • Particularly preferred bisamides are bis-myristoyl-ethylenediamine, bispalmitoyl-ethylenediamine, bis-stearoyl-ethylenediamine and mixtures thereof and the corresponding derivatives of hexamethylenediamine.
  • Also suitable are hexamethylenediamine ethoxylates.
  • the aforementioned ingredients may optionally be part of the particles, granules and / or detergents or cleaners according to the invention.
  • compositions according to the invention can preferably be mixed with further constituents, in particular detergents, care agents and / or cleaning agents or cosmetic ingredients. It is generally known from the broad state of the art which ingredients of washing, care or cleaning agents and which raw materials can usually still be added.
  • the agent may comprise UV absorbers, which are advantageously applied to the treated fabrics and improve the lightfastness of the fibers and / or the lightfastness of other formulation ingredients.
  • UV absorber are organic substances (sunscreen) to understand, which are able to absorb ultraviolet rays and the absorbed energy in the form of longer-wave radiation, eg heat to give back.
  • Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position.
  • substituted benzotriazoles phenyl-substituted acrylates (cinnamic acid derivatives) in the 3-position, optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.
  • the biphenyl and especially stilbene derivatives commercially available as Tinosorb ® FD or Tinosorb ® FR available ex Ciba.
  • Suitable UV-B absorbers are 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, eg 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 2- (dimethylamino) benzoic acid 2-ethylhexyl ester, 4- (dimethylamino) benzoic acid 2-octyl ester and A- (dimethylamino) benzoic acid amyl ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, 4-methoxycinnamic acid propyl ester, 4-methoxycinnamic acid iso-anyl ester, 2-cyano-3,3-phenylcinnamic acid 2-ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl
  • 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts
  • Sulfonic acid derivatives of 3-Benzylidencamphers such as 4- (2-oxo-3-boryl-nylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.
  • UV-A filter in particular derivatives of benzoylmethane come into question, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1, 3-dione, 4-tert-butyl -4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1, 3-dione and enamine compounds.
  • the UV-A and UV-B filters can also be used in mixtures.
  • insoluble photoprotective pigments namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose.
  • suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
  • silicates (talc) barium sulfate or zinc stearate can be used.
  • the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
  • the particles should have an average diameter of less than 100 nm, preferably from 5 to 50 nm and in particular from 15 to 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape.
  • the pigments can also be surface treated, i. hydrophilized or hydrophobized.
  • Typical examples are coated titanium dioxides, e.g. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck).
  • Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the relevant prior art.
  • the UV absorbers may advantageously be contained in the composition in amounts of from 0.01% to 5% by weight, preferably from 0.03% to 1% by weight. They can also be added to the product later, for example together with other substances. In a preferred embodiment, however, the particles according to the invention, granules and / or detergents or cleaners are free of UV absorber or UV-A filter.
  • the detergents or cleaners according to the invention may preferably also be in the form of tablets or shaped articles.
  • tablette or “shaped bodies” are dimensionally stable, solid bodies, irrespective of the manner of their preparation. Such bodies can be, for example, by crystallization, molding, injection molding, reactive or thermal sintering, (co) extrusion, Verprillung, pastillation, or
  • make compaction processes such as calendering or tableting.
  • the preparation of the "tablets" or “shaped bodies” by tabletting is particularly preferred in the context of the present application.
  • the tablet is thus preferably made of compressed, particulate material.
  • Detergents or cleaning agents according to the invention may preferably contain disintegration aids.
  • Suitable swellable disintegration aids are, for example, bentonites or other swellable silicates. It is also possible to use synthetic polymers, in particular the superabsorbents or cross-linked polyvinylpyrrolidone used in the hygiene sector.
  • polymers based on starch and / or cellulose are used as swellable disintegration aids.
  • These base substances can be processed alone or in mixture with other natural and / or synthetic polymers to swellable disintegrating agents.
  • a cellulosic material or pure cellulose can be converted by pressure transfer into secondary particles by granulation, compaction or other application, which swell on contact with water and thus serve as a disintegrant.
  • Wood pulp which has been made available by thermal or chemical-thermal processes from wood or wood shavings (sawdust, sawmill waste) has proved to be suitable as cellulose-containing material.
  • This cellulosic material from the TMP process (thermo-mechanical pulp) or the CTMP process (chemo-thermo-mechanical pulp) can then be compacted by application of pressure, preferably roll-compacted and converted into particle form.
  • pure cellulose can also be used in a completely analogous manner, although it is more expensive from the raw material base.
  • both microcrystalline and amorphous finely divided cellulose and mixtures thereof can be used.
  • the primary fiber length of the cellulose or cellulose used in the cellulosic material should be less than 200 .mu.m, preference being given to primary fiber lengths of less than 100 .mu.m, in particular less than 50 .mu.m.
  • the secondary particles ideally have a particle size distribution in which preferably more than 90 wt .-% of the particles have sizes above 200 microns.
  • a certain proportion of dust can contribute to an improved storage stability of the tablets produced therewith. Shares of a fine dust content of less than 0.1 mm up to 10 wt .-%, preferably up to 8 wt .-% may be present in the agents used in the invention with disintegrant granules.
  • gemini surfactants come into consideration. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called “spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer tris sulfates and ether sulfates.
  • End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing, care or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides, as described in the relevant prior art.
  • surfactants are polyhydroxy fatty acid amides of the following formula
  • RCO is an aliphatic acyl group having 6 to 22 carbon atoms
  • R 23 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are known substances, usually by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride can be obtained.
  • the group of polyhydroxy fatty acid amides also includes compounds of the following formula
  • R 24 is -OR 25
  • R is a linear or branched alkyl or alkenyl group having 7 to 12 carbon atoms
  • R 24 is a linear, branched or cyclic alkyl group or an aryl group containing 2 to 8 carbon atoms
  • R 25 is a linear, branched or cyclic alkyl group or an aryl group or an oxyalkyl radical having from 1 to 8 carbon atoms
  • 4- alkyl or phenyl radicals are preferred
  • [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example, by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • N-methylglucamides are also suitable.
  • the agents according to the invention preferably also contain amphoteric surfactants.
  • the betaines represent an important class.
  • Betaines are known surfactants which are predominantly produced by carboxyalkylation, preferably carboxymethylation of aminic compounds.
  • the starting materials are condensed with halocarboxylic acids or their salts, in particular with sodium chloroacetate, wherein one mole of salt is formed per mole of betaine.
  • unsaturated carboxylic acids such as acrylic acid is possible.
  • betaines are the carboxyalkylation products of secondary and in particular tertiary amines which follow the formula (IX) R 27
  • R 26 is alkyl and / or alkenyl radicals having 6 to 22 carbon atoms
  • R 27 is hydrogen or alkyl radicals having 1 to 4 carbon atoms
  • R 28 is alkyl radicals having 1 to 4 carbon atoms
  • n is a number from 1 to 6 and X is 1 represents an alkali and / or alkaline earth metal or ammonium.
  • Typical examples are the carboxymethylation products of hexylmethylamine, hexyldimethylamine, octyldimethylamine, decyldimethylamine, dodecylmethylamine, dodecyldimethylamine, Dodecylethylmethylamin, C 12 / i 4 -Kokosalkyldimethylamin, myristyldimethylamine, cetyldimethylamine, stearyldimethylamine, Stearylethyl-methyl amine, oleyl dimethyl amine, Ci 6 / i 8 tallow alkyl dimethyl amine, and their technical mixtures.
  • R 31 is CO for an aliphatic acyl radical having 6 to 22 carbon atoms and 0 or 1 to 3 double bonds
  • m is a number from 1 to 3 and R 29 , R 30 , n and X 2 are as defined above.
  • Typical examples are reaction products of fatty acids having 6 to 22 carbon atoms, namely caproic, caprylic, capric, lauric, myristic, palmitic, palmitic, stearic, isostearic, oleic, elaidic, petroselinic, linoleic, linolenic, elaeostearic, and arachidic acids , Gadoleic acid, behenic acid and erucic acid and technical mixtures thereof, with N, N-dimethylaminoethylamine, N, N-dimethylaminopropylamine, N, N-diethylaminoethylamine and N, N-diethylaminopropylamine, which are condensed with sodium chloroacetate.
  • Preference is given to the use of a condensation product of C 8 / i 8 coconut fatty acid N, N-dimethylaminopropylamide with sodium chloroacetate.
  • R 32 is an alkyl radical having 5 to 21 carbon atoms
  • R 33 is a hydroxyl group
  • These substances are also known substances which can be obtained, for example, by cyclizing condensation of 1 or 2 moles of fatty acid with polyhydric amines, such as, for example, aminoethyl-ethanolamine (AEEA) or diethylenetriamine.
  • AEEA aminoethyl-ethanolamine
  • the corresponding carboxyalkylation products are mixtures of different open-chain betaines.
  • Typical examples are condensation products of the above mentioned fatty acids with AEEA, preferably imidazolines based on lauric acid or turn Ci 2 / i 4 coconut oil fatty acid, which are subsequently betainized with sodium chloroacetate.
  • Solvents that may be present in the compositions according to the invention are derived, for example, from the group of monohydric or polyhydric alcohols, alkanolamines or glycol ethers.
  • the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl- or butyldiglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether , Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, butoxy-propoxy-propanol (BPP), dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl, or
  • glycol ethers are available under the trade name Arcosolv ® (Arco Chemical Co.) or Cellosolve ®, carbitol ® or Propasol ® (Union Carbide Corp.); this includes for example ButylCarbitol® ®, hexyl carbitol ®, MethylCarbitol® ®, and carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • Arcosolv ® Arco Chemical Co.
  • Cellosolve ® Cellosolve ®
  • Carbitol ® or Propasol ® Union Carbide Corp.
  • ButylCarbitol® ® hexyl carbitol ®
  • MethylCarbitol® ® MethylCarbitol®
  • carbitol ® itself, (2- (2-ethoxy) ethoxy) ethanol.
  • the choice of glycol ether can be readily made by one skilled in the art on the
  • Pyrrolidone solvent such as N-alkylpyrrolidones, for example N-methyl-2-pyrrolidone or NC 8 -C 2 - alkyl-pyrrolidone or 2-pyrrolidone, may also be employed.
  • glycerol derivatives in particular glycerol carbonate.
  • alcohols which may be included in the compositions of the present invention are low molecular weight liquid polyethylene glycols, for example, polyethylene glycols having a molecular weight of 200, 300, 400 or 600.
  • suitable cosolvents are others Alcohols, for example (a) lower alcohols such as ethanol, propanol, isopropanol and n-butanol, (b) ketones such as acetone and methyl ethyl ketone, (c) C 2 -C 4 polyols such as a diol or a triol, for example ethylene glycol, propylene glycol , Glycerol or mixtures thereof. Particularly preferred is from the class of diols 1, 2-octanediol.
  • the inventive composition contains one or more solvents from the group comprising C 1 - to C 4 -Monoalko-hole, C 2 - to C 6 glycols, C 3 - to C 12 - glycol ethers, and glycerin, in particular ethanol ,
  • the C 3 - to C 12 glycol ethers according to the invention contain alkyl or alkenyl groups having less than 10 carbon atoms, preferably up to 8, in particular up to 6, more preferably 1 to 4 and most preferably 2 to 3 carbon atoms.
  • Preferred C 1 to C 4 monoalcohols are ethanol, n-propanol, / so-propanol and terf-butanol.
  • Preferred C 2 to C 6 glycols are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 5-pentanediol, neopentyl glycol and 1, 6-hexanediol, in particular ethylene glycol and 1, 2-propylene glycol.
  • Preferred C 3 - to C 12 glycol ethers are di-, tri-, tetra- and pentaethylene glycol, di-, tri- and tetrapropylene glycol, propylene glycol monotertiary butyl ether and propylene glycol monoethyl ether and the solvents designated according to INCI butoxydiglycol, butoxyethanol, butoxyisopropanol, butoxypropanol, butyloctanol, Ethoxydiglycol, ethoxyethanol, ethyl hexanediol, isobutoxypropanol, isopentyldiol, 3-methoxybutanol, methoxyethanol, methoxyisopropanol and methoxymethylbutanol.
  • the agent according to the invention can contain one or more solvents only in such amounts that it is still a solid.
  • the agent according to the invention may optionally contain one or more complexing agents.
  • Complexing agents are ingredients that are able to complex and inactivate metal ions.
  • the following complexing agents designated according to INCI are suitable: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Citric Acid, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium Citrate, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactic Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclodextrin, Pentapotassium Triphosphate, Pentasodium Aminotrimethylene Phosphonates, Pentasodium Ethylenediamines Tetramethylene Phosphonates, Pentasodium Pentetates, Pentasoso
  • Preferred complexing agents are tertiary amines, in particular tertiary alkanolamines (amino alcohols).
  • the alkanolamines have both amino and hydroxy and / or ether groups as functional groups.
  • Particularly preferred tertiary alkanolamines are tri-ethanolamine and tetra-2-hydroxypropyl-ethylenediamine (N, N, N ', N'-tetrakis (2-hydroxy-propyl) ethylenediamine).
  • a particularly preferred complexing agent is etidronic acid (1-hydroxyethylidene-1, 1-diphosphonic acid, 1-hydroxyethyl-1, 1-diphosphonic acid, HEDP, acetophosphonic acid, INCI Etidronic Acid) including their salts.
  • the agent according to the invention accordingly contains etidronic acid and / or one or more of its salts as complexing agent.
  • the agent according to the invention contains a complexing agent combination of one or more tertiary amines and one or more further complexing agents, preferably one or more complexing acids or salts thereof, in particular triethanolamine and / or tetra-2-hydroxypropylethylenediamine and etidronic acid and / or one or more several of their salts.
  • the washing or cleaning agent according to the invention advantageously contains complexing agents in an amount of usually 0 to 20 wt .-%, preferably 0.1 to 15 wt .-%, in particular 0.5 to 10 wt .-%, particularly preferably 1 to 8 wt .-%, most preferably 1, 5 to 6 wt .-%, based on the total washing or cleaning agent.
  • the agent according to the invention optionally contains one or more enzymes.
  • Particularly suitable enzymes are those from the classes of hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains and graying.
  • cellulases and other glycosyl hydrolases may contribute to color retention and to enhancing the softness of the fabric by removing pilling and microfibrils. Oxireductases can also be used for bleaching or inhibiting color transfer.
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and Lipase.
  • lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • cellulases are preferably cellobiohydrolases, endoglucanases and ß-glucosidases, which are also called cellobiases, or mixtures thereof used. Since different cellulase types differ by their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases. It is particularly advantageous if the agents according to the invention contain mannanase. This corresponds to a preferred embodiment of the invention. It could be found that the mannanase in combination with the photocatalytic material gave a particularly good effect in the soil removal of galactomannan restroomn residues. The use of tannase is also preferred.
  • the enzymes may be adsorbed as a shaped body to carriers or embedded coated to protect against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.12 to about 2 wt .-%, based on the total washing or cleaning agent.
  • the agents according to the invention may contain bleaching agents.
  • bleaching agents Among those serving as bleach, in water H 2 O 2 supplying compounds have the sodium percarbonate, the sodium perborate tetrahydrate and the sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as persulfates or persulfuric acid.
  • the urea peroxohydrate percarbamide represented by the formula H 2 N-CO-NH 2 2 O 2 can be described H.
  • the means for cleaning hard surfaces for example in automatic dishwashing, they may, if desired, also contain bleaching agents from the group of organic bleaches, although their use is also possible in principle for laundry detergents.
  • Typical organic bleaches are the diacyl peroxides, such as dibenzoyl peroxide.
  • Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • Preferred representatives are the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid (Phthalimidoperoxyhexanoic acid, PAP), o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonylamidopersuccinates, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxy carboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyl-diperoxybutano-1,4-
  • the bleaching agents may preferably be coated to protect against premature decomposition.
  • the washing or cleaning agent according to the invention may preferably contain one or more antimicrobial agents or preservatives in an amount of usually 0.0001 to 3 wt .-%, preferably 0.0001 to 2 wt .-%, in particular 0.0002 to 1 wt. %, more preferably 0.0002 to 0.2% by weight, most preferably 0.0003 to 0.1% by weight.
  • Antimicrobial agents or preservatives are distinguished depending on the antimicrobial spectrum and mechanism of action between bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuriacetate.
  • the terms antimicrobial action and antimicrobial agent have the usual meaning within the scope of the teaching according to the invention.
  • Suitable antimicrobial agents are preferably selected from the groups of the alcohols, amines, aldehydes, antimicrobial acids or their salts, carboxylic acid esters, acid amides, phenols, phenol derivatives, diphenyls, diphenylalkanes, urea derivatives, oxygen, nitrogen acetals and formals, benzamidines, isothiazolines , Phthalimide derivatives, pyridine derivatives, antimicrobial surface-active compounds, guanidines, antimicrobial amphoteric compounds, quinolines, 1, 2-dibromo-2,4-di-cyanobutane, iodo-2-propyl-butyl-carbamate, iodine, iodophores, peroxo compounds, halogen compounds and any mixtures of the above.
  • the antimicrobial agent may be selected from ethanol, n-propanol, i-propanol, 1,3-butanediol, phenoxyethanol, 1,2-propylene glycol, glycerol, undecylenic acid, benzoic acid, salicylic acid, dihydracetic acid, o-phenylphenol, N-propanol.
  • Methylmorpholine-acetonitrile MMA
  • 2-benzyl-4-chlorophenol 2,2'-methylenebis (6-bromo-4-chlorophenol), 4,4'-di-chloro-2'-hydroxydiphenyl ether ( Dichlosan), 2,4,4'-trichloro-2'-hydroxydiphenylether (trichlosan), chlorhexidine, N- (4-chlorophenyl) - N- (3,4-dichlorophenyl) -urea, N, N '- (1, 10-decanediyldi-1-pyridinyl-4-ylidene) bis- (1-octanamine) dihydrochloride, N, N'-bis (4-chlorophenyl) -3,12-diimino-2,4,11, 13-tetraaza-tetradecandiinnidanide, glucoprotamines, antimicrobial surface-active quaternary compounds, guanidines,
  • halogenated xylene and cresol derivatives such as p-chloromethacresol or p-chlorometaxylene, and natural antimicrobial agents of plant origin (for example, from spices or herbs), of animal and microbial origin.
  • antimicrobial surface-active quaternary compounds a natural antimicrobial agent of plant origin and / or a natural antimicrobial agent of animal origin, most preferably at least one natural antimicrobial agent of plant origin from the group comprising caffeine, theobromine and theophylline and essential oils such as eugenol, thymol and geraniol, and / or at least one natural antimicrobial agent of animal origin from the group, comprising enzymes such as protein from milk, lysozyme and lactoperoxidase, and / or at least one antimicrobial surface-active quaternary compound with an ammonium, sulfonium, phosphonium, iodonium - or Arsonium distr, peroxo compounds and chlorine compounds are used. Also substances of microbial origin, so-called bacteriocins, can be used. Glycine, glycine derivatives, formaldehyde, compounds which readily split off formaldehyde, formic acid and peroxide
  • quaternary ammonium compounds have been described above. Is particularly suitable, for example, benzalkonium chloride, etc. Benzalkonium halides and / or substituted benzalkonium halides are for example commercially available as Barquat ® ex Lonza, Marquat® ® ex Mason, Variquat ® ex Witco / Sherex and Hyamine ® ex Lonza and as Bardac ® ex Lonza.
  • antimicrobial agents are N- (3-chloroallyl) hexaminium chloride such as Dowicide and Dowicil ® ® ex Dow, benzethonium chloride such as Hyamine ® 1622 ex Rohm & Haas, methylbenzethonium as Hyamine ® 1ox ex Rohm & Haas, cetylpyridinium chloride such as Cepacol ex Merrell Labs ,
  • the agents according to the invention may optionally contain ironing aids for improving the water absorption capacity, the rewettability of the treated textiles and for ease of ironing the treated textiles.
  • ironing aids for improving the water absorption capacity, the rewettability of the treated textiles and for ease of ironing the treated textiles.
  • silicone derivatives can be used in the formulations. These additionally improve the rinsing out of the wash-active formulations by their foam-inhibiting properties.
  • Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated.
  • Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.
  • the compositions according to the invention may preferably also be perfumed with perfume oil (fragrances, fragrances).
  • perfume oil preferably self-contained perfume compositions which are commonly used for product scenting and are fragrant in particular at the human discretion. This will be explained with an example. If an expert wants to fragrant with a shower gel, he usually adds to it not only a (well) smelling substance but a collective (well) smelling substance. Such a collective usually consists of a plurality of individual fragrances, e.g. more than 10 or 15, preferably up to 100 or more. These resources interactively form a desired fragrant, harmonious odor image.
  • a perfume oil according to the invention may contain individual perfume compounds, e.g. containing the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance compounds of the ester type are known e.g.
  • the ethers include, for example, benzyl ethyl ether and ambroxane, to the aldehydes e.g.
  • the linear alkanals of 8 - 18 C atoms citral, citronellal, citronellyloxy-acetaldehyde, cyclamen aldehyde, lilial and bourgeonal, to the ketones e.g. the ionones, ° c-
  • the perfume oils can also contain natural fragrance mixtures, such as those available from plant sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are Muskateller sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange blossom oil, neroliol, orange peel oil and sandalwood oil.
  • a fragrance In order to be perceptible, a fragrance must be volatile, with molecular weight also playing an important role in addition to the nature of the functional groups and the structure of the chemical compound.
  • odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a fragrance composed of several fragrances changes during evaporation, wherein the Odor sensations divided into "top note”, “middle note or body” and “base note” (end note or dry out).
  • Adhesive-resistant fragrances which are advantageously usable in the perfume oils in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, Bay oil, Champacablütenöl, Edeltannöl, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, Ginger Grass Oil, Guajac Wood Oil, Gurjun Balm Oil, Helichrysum Oil, Ho Oil, Ginger Oil, Iris Oil, Cajeput Oil, Calam Oil, Chamomile Oil, Camphor Oil, Kanaga Oil, Cardamom Oil, Cassia Oil, Pine Needle Oil, Kopa ⁇ vabalsam Oil, Coriander Oil, Spearmint Oil, Cumin Oil, Cumin Oil, Lemongrass Oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli oil, Niaouli oil, Olibanum oil
  • fragrances of natural or synthetic origin can be used in the context of the present invention advantageously as adherent fragrances or fragrance mixtures in the perfume oils.
  • These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, borneol, bornyl acetate, ⁇ -bromostyrene, n -Decylaldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl
  • fragrances which are advantageously used in the perfume oil in the present invention include, in particular, the lower-boiling fragrances natural or synthetic origin, which can be used alone or in mixtures.
  • fragrances examples include alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, Linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
  • fragrances from the group of allyl alcohol esters, esters of secondary alcohols, esters of tertiary alcohols, allylic ketones, acetals, ketals, condensation products of amines and aldehydes and / or mixtures thereof may be included in the perfume oil.
  • the composition according to the invention contains certain minimum values of perfume oil, namely at least 0.00001% by weight, advantageously at least 0.0001% by weight, considerably advantageously at least 0.001% by weight, more preferably at least 0, 01 wt .-%, in a further advantageous manner at least 0.1 wt .-%, more preferably at least 0.2 wt .-%, in a very advantageous manner at least 0.3 wt .-%, in a particularly advantageous manner at least 0.4% by weight, in a particularly advantageous manner at least 0.45% by weight, in a significantly advantageous manner at least 0.5% by weight, in a remarkably advantageous manner at least 0.55% by weight, in an extremely advantageous manner at least 0.6% by weight, most advantageously at least 0.65% by weight, most advantageously at least 0.7% by weight, in an exceptionally advantageous manner at least 0.75% by weight, in extraordinarily advantageous manner, at least 0.8% by weight, in extremely advanced advantageously at least 0.85 wt .-%, in particular at least 0.9 w
  • the perfume oils contain less than 8, advantageously less than 7, more preferably less than 6, more preferably less than 5, more preferably less than 4, even more preferably less than 3, preferably less than 2, especially no fragrances from the list Amylcinnamal, Amylcinnamylalkohol, Benzylalcohol, Benzylsalicylat, Cinnamylalkohol, Cinnamal, Citral, Cumarin, Eugenol, Geraniol, Hydroxycitronellal, Hydroxymethylpentylcyclohexencarboxaldehyde, Isoeugenol, Anisylalkohol, Benzylbenzoat, Benzylcinnamat, Citronellol, Farnesol, Hexylcinnamaldehyd, Lilial, d-Limonen, Linalool , Methylheptincarbonate, 3-methyl-4- (2,6,6-trimethyl-2-cyclohexen-1-yl)
  • the agent according to the invention can be free of perfume oil.

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Abstract

L'invention concerne des particules contenant un matériau photocatalytique. Elle décrit des particules et des granulés contenant un matériau photocatalytique, qui peuvent servir d'agents de lavage ou de nettoyage ou peuvent au moins être employés dans de tels agents. L'emploi de ces particules et de ces granulés permet l'élimination, la désactivation ou la diminution d'impuretés et de micro-organismes, en particulier de bactéries et de germes, dans des textiles, par exposition à de la lumière dans la plage de longueurs d'onde allant de 10 à 1200 nm. Il permet de détacher plus facilement la saleté colorée (les taches de couleurs) des textiles, il permet de réduire l'adhérence de la saleté aux fibres, de préférence des taches de couleurs, se trouvant sur des textiles, il permet d'augmenter la solubilité dans l'eau de la saleté, de préférence des taches de couleurs, se trouvant sur des textiles, il permet de prévenir l'apparition de mauvaises odeurs sur les textiles et il permet de doter les textiles d'un pouvoir autonettoyant, à chaque fois par exposition à de la lumière dans la plage de longueurs d'onde allant de 10 à 1200 nm.
PCT/EP2008/052996 2007-04-23 2008-03-13 Particules contenant un matériau photocatalytique Ceased WO2008128826A1 (fr)

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US11312922B2 (en) 2019-04-12 2022-04-26 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner comprising a sulfonic acid-containing surfactant and methods of making and using the same
EP3497195B1 (fr) 2016-08-10 2022-09-07 Unilever IP Holdings B.V. Composition de lavage
US11679065B2 (en) 2020-02-27 2023-06-20 The Procter & Gamble Company Compositions with sulfur having enhanced efficacy and aesthetics
US11771635B2 (en) 2021-05-14 2023-10-03 The Procter & Gamble Company Shampoo composition
US11819474B2 (en) 2020-12-04 2023-11-21 The Procter & Gamble Company Hair care compositions comprising malodor reduction materials
US11904036B2 (en) 2017-10-10 2024-02-20 The Procter & Gamble Company Sulfate free clear personal cleansing composition comprising low inorganic salt
US11980679B2 (en) 2019-12-06 2024-05-14 The Procter & Gamble Company Sulfate free composition with enhanced deposition of scalp active
US11986543B2 (en) 2021-06-01 2024-05-21 The Procter & Gamble Company Rinse-off compositions with a surfactant system that is substantially free of sulfate-based surfactants
US12427099B2 (en) 2020-11-23 2025-09-30 The Procter & Gamble Company Personal care composition
US12458575B2 (en) 2021-12-09 2025-11-04 The Procter & Gamble Company Sulfate free personal cleansing composition comprising effective preservation

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CN102383319B (zh) * 2011-06-16 2013-04-17 北京泛博化学股份有限公司 一种增深剂及其制备方法
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CN104294687A (zh) * 2014-09-27 2015-01-21 无锡市东北塘宏良染色厂 一种白地防沾污剂
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CN103979573A (zh) * 2014-06-01 2014-08-13 许盛英 酸化后的沸石
EP3497195B1 (fr) 2016-08-10 2022-09-07 Unilever IP Holdings B.V. Composition de lavage
US11992540B2 (en) 2017-10-10 2024-05-28 The Procter & Gamble Company Sulfate free personal cleansing composition comprising low inorganic salt
US11904036B2 (en) 2017-10-10 2024-02-20 The Procter & Gamble Company Sulfate free clear personal cleansing composition comprising low inorganic salt
US11312922B2 (en) 2019-04-12 2022-04-26 Ecolab Usa Inc. Antimicrobial multi-purpose cleaner comprising a sulfonic acid-containing surfactant and methods of making and using the same
US12480071B2 (en) 2019-04-12 2025-11-25 Ecolab Usa Inc. Acidic antimicrobial multi-purpose cleaner with a sulfonate anionic surfactant and phenoxyethanol mixture
US11891586B2 (en) 2019-04-12 2024-02-06 Ecolab Usa Inc. Highly acidic antimicrobial multi-purpose cleaner and methods of making and using the same
US11980679B2 (en) 2019-12-06 2024-05-14 The Procter & Gamble Company Sulfate free composition with enhanced deposition of scalp active
US11679065B2 (en) 2020-02-27 2023-06-20 The Procter & Gamble Company Compositions with sulfur having enhanced efficacy and aesthetics
US12427099B2 (en) 2020-11-23 2025-09-30 The Procter & Gamble Company Personal care composition
US11819474B2 (en) 2020-12-04 2023-11-21 The Procter & Gamble Company Hair care compositions comprising malodor reduction materials
US12409125B2 (en) 2021-05-14 2025-09-09 The Procter & Gamble Company Shampoo compositions containing a sulfate-free surfactant system and sclerotium gum thickener
US11771635B2 (en) 2021-05-14 2023-10-03 The Procter & Gamble Company Shampoo composition
US11986543B2 (en) 2021-06-01 2024-05-21 The Procter & Gamble Company Rinse-off compositions with a surfactant system that is substantially free of sulfate-based surfactants
US12458575B2 (en) 2021-12-09 2025-11-04 The Procter & Gamble Company Sulfate free personal cleansing composition comprising effective preservation

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